JP2009173550A - Method for producing hydrogenolysis product of polyhydric alcohol - Google Patents
Method for producing hydrogenolysis product of polyhydric alcohol Download PDFInfo
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- JP2009173550A JP2009173550A JP2008010676A JP2008010676A JP2009173550A JP 2009173550 A JP2009173550 A JP 2009173550A JP 2008010676 A JP2008010676 A JP 2008010676A JP 2008010676 A JP2008010676 A JP 2008010676A JP 2009173550 A JP2009173550 A JP 2009173550A
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- polyhydric alcohol
- reaction
- water
- glycerin
- copper
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- 150000005846 sugar alcohols Polymers 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000012071 phase Substances 0.000 claims abstract description 20
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 83
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 239000003054 catalyst Substances 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 20
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 235000013772 propylene glycol Nutrition 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 12
- 238000004517 catalytic hydrocracking Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 8
- -1 copper-iron-aluminum Chemical compound 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- 238000003109 Karl Fischer titration Methods 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- TYYRFZAVEXQXSN-UHFFFAOYSA-H aluminium sulfate hexadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O TYYRFZAVEXQXSN-UHFFFAOYSA-H 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 235000010355 mannitol Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- GFCDJPPBUCXJSC-UHFFFAOYSA-N [O-2].[Zn+2].[Cu]=O Chemical compound [O-2].[Zn+2].[Cu]=O GFCDJPPBUCXJSC-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical class CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- VODBHXZOIQDDST-UHFFFAOYSA-N copper zinc oxygen(2-) Chemical compound [O--].[O--].[Cu++].[Zn++] VODBHXZOIQDDST-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- FNTHQRXVZDCWSP-UHFFFAOYSA-N cyclohexane-1,1,2-triol Chemical class OC1CCCCC1(O)O FNTHQRXVZDCWSP-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical class OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical class CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical class CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- UJRJCSCBZXLGKF-UHFFFAOYSA-N nickel rhenium Chemical compound [Ni].[Re] UJRJCSCBZXLGKF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- FVGBHSIHHXTYTH-UHFFFAOYSA-N pentane-1,1,1-triol Chemical class CCCCC(O)(O)O FVGBHSIHHXTYTH-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical class CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J25/00—Catalysts of the Raney type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、多価アルコールを効率的に転化させ、その水素化分解物を選択性良く製造する方法に関する。 The present invention relates to a method for efficiently converting a polyhydric alcohol and producing a hydrocracked product thereof with high selectivity.
自然界から得られる多価アルコールを、触媒を利用して水素化分解を行い、他の化合物に変換することは、物質の有効利用の観点から重要である。
一方、多価アルコールとして、食品や医療などに使用されているグリセリンは、年々生産量を増やしてきている。その理由として、化石化燃料の供給不安や、地球温暖化問題を背景にして延びてきた、バイオディーゼル燃料の普及が挙げられる。植物原料から製造されるバイオディーゼル燃料はその製造過程でグリセリンを生成する。しかしながら、現状ではグリセリンの用途は限られていることから、供給過剰になりつつあり、その有効利用が求められている。その一つとして触媒反応を用いたC3アルコール類への変換が世界的に注目されている。
It is important from the viewpoint of effective utilization of substances to convert polyhydric alcohols obtained from nature to other compounds by hydrocracking using a catalyst.
On the other hand, glycerin, which is used as a polyhydric alcohol in foods and medicine, has been increasing in production year by year. The reasons for this include the fear of supplying fossil fuels and the widespread use of biodiesel fuel, which has been growing against the background of global warming. Biodiesel fuel produced from plant raw materials produces glycerin during the production process. However, since the use of glycerin is limited at present, the supply is becoming excessive and its effective use is required. As one of them, conversion to C3 alcohols using a catalytic reaction has attracted attention worldwide.
C3アルコール類は、様々な工業原料等として有用である。C3アルコール類の中でもジオール類としては、1,3−プロパンジオール及び1,2−プロパンジオールがあり、1,3−プロパンジオールは、ポリエステル及びポリウレタン原料等として注目されている。
また、1,2−プロパンジオール(以下、「1,2−PD」ということがある)は、例えばポリエステル樹脂、塗料、アルキッド樹脂、各種可塑剤、不凍液、ブレーキオイル等に用いられ、さらには食品保潤剤、果汁粘度増強剤、食品用セロハン柔軟剤、化粧品、医薬品等に有用である。
C3 alcohols are useful as various industrial raw materials. Among the C3 alcohols, diols include 1,3-propanediol and 1,2-propanediol, and 1,3-propanediol is attracting attention as a polyester and polyurethane raw material.
In addition, 1,2-propanediol (hereinafter sometimes referred to as “1,2-PD”) is used in, for example, polyester resins, paints, alkyd resins, various plasticizers, antifreeze liquids, brake oils, and the like. It is useful for humectants, fruit juice viscosity enhancers, cellophane softeners for foods, cosmetics, pharmaceuticals, and the like.
グリセリンの有効利用として、グリセリンを水素化分解して1,2−PDを製造する種々の方法が提案されている。
例えば、触媒として、(1)ニッケル−レニウム/炭素を用いる方法(例えば、特許文献1参照)、(2)ルテニウム/炭素を用いる方法(例えば、特許文献2参照)、(3)銅−亜鉛/アルミナを用いる方法(例えば、特許文献3参照)、(4)銅−酸化亜鉛を用いる方法(例えば、特許文献4参照)、(5)銅−クロムを用いる方法(例えば、非特許文献1参照)、(6)ルテニウムを用いる方法(例えば、特許文献5参照)等が知られている。
しかしながら、これらの方法においては、グリセリンの転化率が低かったり、1,2−PDの選択率が低かったりなどして、充分に満足し得るものではなかった。特に工業的に実施が有利な低圧下では、高反応性と高選択性の両立が難しく、満足し得るものではなかった。また、非特許文献1、および特許文献5には、水の効果について記載されており、水をあらかじめ添加しておかないと選択性が大幅に低下することが記載されている。
As an effective use of glycerin, various methods for producing 1,2-PD by hydrogenolysis of glycerin have been proposed.
For example, as a catalyst, (1) a method using nickel-rhenium / carbon (for example, refer to Patent Document 1), (2) a method using ruthenium / carbon (for example, refer to Patent Document 2), (3) copper-zinc / A method using alumina (for example, see Patent Document 3), (4) a method using copper-zinc oxide (for example, see Patent Document 4), and (5) a method using copper-chromium (for example, see Non-Patent Document 1). (6) A method using ruthenium (see, for example, Patent Document 5) is known.
However, in these methods, the conversion rate of glycerin is low or the selectivity of 1,2-PD is low, so that it is not satisfactory. Particularly under low pressure, which is advantageous industrially, it is difficult to achieve both high reactivity and high selectivity, which is not satisfactory. Non-Patent Document 1 and Patent Document 5 describe the effect of water, and it is described that the selectivity is greatly reduced unless water is added in advance.
本発明は、回分方式の触媒による多価アルコールの水素化分解物の製造方法において、その反応性を向上させることを課題とし、特に多価アルコールとしてグリセリンを用いた場合において、グリセリンの反応性を向上させ、1,2−プロパンジオールへ効率的に変換することを課題とする。 The present invention has an object to improve the reactivity in a method for producing a hydrogenolysis product of a polyhydric alcohol using a batch catalyst, and particularly when glycerin is used as the polyhydric alcohol, the reactivity of glycerin is improved. It is an object to improve and efficiently convert to 1,2-propanediol.
本発明者らは、多価アルコールの水素化分解物の製造方法として、反応の進行に伴い反応液相中に滞留した水を除去しながら反応させることにより、前記課題を解決し得ることを見出した。
すなわち、本発明は、
(1)水素化触媒の存在下に多価アルコールと水素とを接触させて、反応液相中の水を除去しながら反応を行う、回分方式の多価アルコールの水素化分解物の製造方法、
を提供する。
The present inventors have found that the above problem can be solved by removing water remaining in the reaction liquid phase with the progress of the reaction as a method for producing a hydrocracked product of polyhydric alcohol. It was.
That is, the present invention
(1) A process for producing a hydrocracked product of a polyhydric alcohol in a batch system, in which a polyhydric alcohol is brought into contact with hydrogen in the presence of a hydrogenation catalyst, and the reaction is carried out while removing water in the reaction liquid phase;
I will provide a.
本発明によれば、多価アルコールからの水素化分解物を効率的に製造でき、特にグリセリンから1,2−PDを効率的に製造する方法を提供することができる。また、本製造方法を用いることにより、低圧下で、グリセリンを効率的に転化させ、1,2−PDを選択性良く製造できる。 According to the present invention, it is possible to efficiently produce a hydrocracked product from a polyhydric alcohol, and in particular, it is possible to provide a method for efficiently producing 1,2-PD from glycerin. Moreover, by using this production method, glycerol can be efficiently converted under low pressure, and 1,2-PD can be produced with good selectivity.
本発明の多価アルコールの水素化分解物の製造方法においては、水素化分解触媒の存在下に、多価アルコールと水素とを加熱して、該多価アルコールを水素化分解する。
多価アルコールとしては、水酸基数2〜6の化合物が好ましい。具体的には、水酸基数2〜6であって、かつ炭素数2〜60の脂肪族又は脂環式多価アルコールを挙げることができる。具体的にはエチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、各種プロパンジオール、各種ジプロパンジオール、各種トリプロパンジオール、各種ブタンジオール、各種ジブタンジオール、各種ペンタンジオール各種ペンタントリオール、各種ヘキサンジオール、各種ヘキサントリオール、グリセリン、ジグリセリン、トリグリセリン、各種シクロヘキサンジオール、各種シクロヘキサントリオール、ペンタエリスリトール、トリメチロールプロパン、さらにはソルビトールやマンニトール等の糖アルコール等を例示することができる。これらの中では、工業的観点から、グリセリン並びにソルビトール及びマンニトールなどの糖アルコールが好ましく、グリセリンが特に好ましい。
また、本発明における多価アルコールの水素化分解物とは、多価アルコールに水素を作用させて、水酸基を分解させて得られたものであり、少なくとも1つ以上の水酸基を残す程度に分解させて得られる化合物を示す。例えばグリセリン (分子内の水酸基数:3つ)の水素化分解物は、C3ジオール(分子内の水酸基:2つ)、C3モノオール(分子内の水酸基数:1つ)である。
In the method for producing a hydrocracked product of a polyhydric alcohol of the present invention, the polyhydric alcohol and hydrogen are heated in the presence of a hydrocracking catalyst to hydrocrack the polyhydric alcohol.
As the polyhydric alcohol, a compound having 2 to 6 hydroxyl groups is preferable. Specific examples include aliphatic or alicyclic polyhydric alcohols having 2 to 6 hydroxyl groups and 2 to 60 carbon atoms. Specifically, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, various propanediols, various dipropanediols, various tripropanediols, various butanediols, various dibutanediols, various pentanediols, various pentanetriols, various hexanediols, Examples include various hexanetriols, glycerin, diglycerin, triglycerin, various cyclohexanediols, various cyclohexanetriols, pentaerythritol, trimethylolpropane, and sugar alcohols such as sorbitol and mannitol. Among these, glycerin and sugar alcohols such as sorbitol and mannitol are preferable from an industrial viewpoint, and glycerin is particularly preferable.
The hydrocracked product of polyhydric alcohol in the present invention is obtained by causing hydrogen to act on polyhydric alcohol to decompose hydroxyl groups, and decomposes it to the extent that at least one hydroxyl group remains. The compound obtained is shown. For example, hydrogenolysis products of glycerin (number of hydroxyl groups in the molecule: 3) are C3 diol (hydroxyl groups in the molecule: 2) and C3 monool (number of hydroxyl groups in the molecule: 1).
前記水素化分解触媒としては、例えば、銅、ニッケル、コバルト、ルテニウム、パラジウム、白金、ロジウム等から選ばれる少なくとも1種の金属種やこれらの金属原子を含む錯体触媒を用いることができ、またこれら金属種をアルミナ、シリカ、酸化チタン等の担体に担持した固体触媒も用いることができる。その中で、銅含有触媒(「銅触媒」という場合がある)が好ましく、特に銅−鉄−アルミ、銅/シリカ、銅−亜鉛/酸化チタン、及び銅ラネー(Raney)触媒が好ましい。その中でも銅−鉄−アルミ、銅/シリカが好ましく、特に銅/シリカが好ましい。
触媒としては、市販のものを用いてもよく、また、例えば沈殿法、イオン交換法、蒸発乾固法、噴霧乾燥法、混練法等通常採用されている従来公知の方法にて、担体上に金属成分を担持することで調製することができる。
これら触媒の使用量は、原料である多価アルコール100質量部に対して0.01〜20質量部、好ましくは0.1〜10質量部、さらに好ましくは0.3〜6質量部である。
As the hydrocracking catalyst, for example, at least one metal species selected from copper, nickel, cobalt, ruthenium, palladium, platinum, rhodium, etc., and a complex catalyst containing these metal atoms can be used. A solid catalyst in which a metal species is supported on a carrier such as alumina, silica, titanium oxide or the like can also be used. Among them, copper-containing catalysts (sometimes referred to as “copper catalysts”) are preferable, and copper-iron-aluminum, copper / silica, copper-zinc / titanium oxide, and copper Raney catalysts are particularly preferable. Among these, copper-iron-aluminum and copper / silica are preferable, and copper / silica is particularly preferable.
As the catalyst, a commercially available catalyst may be used. For example, a conventionally known method such as a precipitation method, an ion exchange method, an evaporation to dryness method, a spray drying method, a kneading method or the like is used on the carrier. It can be prepared by supporting a metal component.
The usage-amount of these catalysts is 0.01-20 mass parts with respect to 100 mass parts of polyhydric alcohols which are raw materials, Preferably it is 0.1-10 mass parts, More preferably, it is 0.3-6 mass parts.
本発明の多価アルコールの水素化分解物の製造方法においては、反応液相中の水を除去する方法として、水を水蒸気として気相へ誘導する方法や、脱水剤を反応容器内にあらかじめ存在させておき、液相の水分を吸収させる方法が使用できる。水を水蒸気として気相へ誘導する方法では、ガスを流通させ、反応容器外へ誘導することで促進することもでき、この場合には水素、又は窒素、アルゴン等の不活性ガスの1種以上を使用できる。本発明では、ガスを流通させることで促進することが好ましく、水素ガスを反応試剤とすることからガスとしては、水素ガスが好ましい。
水の除去は連続的でなくともよく、水分を反応系内から一部除去するだけで、反応効率は向上する。ここでいう反応効率とは主に反応速度を指し、グリセリンに限っては1,2−プロパンジオールへの変換率もまた意味する。水素化分解では、多価アルコールから水が生成される。回分方式での反応系では水は系内に蓄積されるために、水分量は反応が進むとともに増加する。一方で多価アルコールは減少していく。最終的に生成される全水分量は多価アルコールによって異なるが、反応に用いた多価アルコールの量から求めることができる。本発明では水を除去する条件として、反応液相中の多価アルコールが60モル%反応した時点から、換言すると残存多価アルコール量が40モル%になった時点から、反応終了までの何れかの時点で、多価アルコールから生じる全水分量を1とするときの割合(以下、「水分率」という場合がある。)が0.5以下、好ましくは0.4以下、特に好ましくは0.3以下になるように、反応液相中の水を除去することがよい。反応系内の水は少ない方がよく、連続的に水分を反応系外に追い出すことが好ましい。反応当初から水分を除去するためには、上記したガスを流通させる方法で水分を反応液相中から除去することが好ましい。数値上では、反応液相中の多価アルコールが60モル%反応した時点以後は、反応液相中の水分の割合は、多価アルコールから生じる全水分量を1として0.5以下、更には0.4以下、特には0.3以下に保つことが好ましい。
特に、グリセリンからの1,2−プロパンジオールへの変換において、液相中の水分量が少ないほどグリセリンの反応性が向上する。水分量は、経時的にサンプルを抜き出し、カールフィッシャー分析を行い、算出することができる。
In the method for producing a hydrolyzate of a polyhydric alcohol of the present invention, as a method for removing water in the reaction liquid phase, a method for inducing water into the gas phase as water vapor, or a dehydrating agent is present in the reaction vessel in advance. In addition, a method of absorbing liquid phase moisture can be used. In the method of inducing water as water vapor into the gas phase, gas can be circulated and promoted by inducing out of the reaction vessel. In this case, one or more of inert gases such as hydrogen, nitrogen, and argon are used. Can be used. In this invention, it is preferable to promote by circulating gas, and since hydrogen gas is used as a reaction reagent, hydrogen gas is preferable.
The removal of water does not have to be continuous, and the reaction efficiency is improved by removing a part of the water from the reaction system. The reaction efficiency here mainly refers to the reaction rate, and in the case of glycerin, it also means the conversion rate to 1,2-propanediol. In hydrocracking, water is produced from polyhydric alcohols. In a batch reaction system, water is accumulated in the system, so that the amount of water increases as the reaction proceeds. On the other hand, polyhydric alcohol decreases. The total amount of water finally produced varies depending on the polyhydric alcohol, but can be determined from the amount of polyhydric alcohol used in the reaction. In the present invention, the condition for removing water is any time from when the polyhydric alcohol in the reaction liquid phase has reacted 60 mol%, in other words, from the time when the amount of residual polyhydric alcohol has reached 40 mol% to the end of the reaction. When the total water content generated from the polyhydric alcohol is 1, the ratio (hereinafter sometimes referred to as “moisture ratio”) is 0.5 or less, preferably 0.4 or less, particularly preferably 0.8. It is preferable to remove water in the reaction liquid phase so as to be 3 or less. The amount of water in the reaction system should be small, and it is preferable to continuously expel water from the reaction system. In order to remove the water from the beginning of the reaction, it is preferable to remove the water from the reaction liquid phase by a method of circulating the gas described above. In terms of numerical values, after the time when 60 mol% of the polyhydric alcohol in the reaction liquid phase has reacted, the proportion of water in the reaction liquid phase is 0.5 or less, where 1 is the total water content generated from the polyhydric alcohol, It is preferable to keep it at 0.4 or less, particularly 0.3 or less.
In particular, in the conversion of glycerin to 1,2-propanediol, the smaller the amount of water in the liquid phase, the better the reactivity of glycerin. The amount of water can be calculated by extracting a sample over time and performing Karl Fischer analysis.
反応条件については特に制限はなく、使用する多価アルコールや触媒の種類等に応じて適宣選定される。水素圧は、通常、常温で30MPa以下が好ましく、工業化の観点からより低圧である0.1〜10MPaが好ましく、0.5〜5MPaがより好ましく、0.5〜3MPaがさらに好ましい。反応温度は、通常80℃以上で水素化分解を実施することができるが、多価アルコールの水素化分解による転化率及び分解生成物の選択性等の観点から、130〜350℃の範囲が好ましく、160〜300℃の範囲がより好ましく、180〜250℃の範囲が特に好ましい。
水素化分解反応の反応装置としては、オートクレーブ等の加圧可能な装置を用いた回分式(バッチ式)が好ましい。
There are no particular restrictions on the reaction conditions, and the reaction conditions are appropriately selected according to the type of polyhydric alcohol and catalyst used. The hydrogen pressure is usually preferably 30 MPa or less at normal temperature, preferably 0.1 to 10 MPa, more preferably 0.5 to 5 MPa, and further preferably 0.5 to 3 MPa, from the viewpoint of industrialization. The reaction temperature can usually be hydrocracked at 80 ° C. or higher, but is preferably in the range of 130 ° C. to 350 ° C. from the viewpoint of the conversion rate of the polyhydric alcohol by hydrogenolysis and the selectivity of the decomposition products. The range of 160 to 300 ° C is more preferable, and the range of 180 to 250 ° C is particularly preferable.
As a reaction apparatus for the hydrocracking reaction, a batch system using a pressurizable apparatus such as an autoclave is preferable.
本発明の多価アルコール水素化分解物の製造方法においては、多価アルコールとしてグリセリンを用いることが好ましい。このグリセリンを用いることにより、水素化分解物として、1,2−PDを効率的に製造することができる。 In the method for producing a polyhydric alcohol hydrolyzate of the present invention, glycerin is preferably used as the polyhydric alcohol. By using this glycerin, 1,2-PD can be efficiently produced as a hydrocracked product.
実施例1
(銅−鉄−アルミニウム系触媒の調製)
下記の操作を行い、銅/鉄/アルミニウムの原子比が1/0.8/1.8である銅−鉄−アルミニウム系触媒を製造した。
還流冷却器を有する反応器に、水(300g)、CuSO4・5H2O(48g)、FeSO4・7H2O(46.8g)及び水酸化アルミニウム(12.8g)を入れ、撹拌しながら温度を96℃に上昇させた。温度を95±2℃に保ちながら1時間保持した。次いでこの温度を保ちながら、Na2CO3(44.8g)を水(150g)に溶解させた溶液を約80分かけて滴下した。温度を95±2℃に保ちながら、CuSO4・5H2O(4.8g)、Al2(SO4)3・16H2O(46.8g)を水(109.2g)に溶解させた溶液と、Na2CO3(27.6g)を水(98.2g)に溶解させた溶液を同時に滴下した。金属塩の水溶液は60分、アルカリ物質の水溶液は30分かけて滴下した。これにAl2(SO4)3・16H2O(23.4g)を水(53.5g)に溶解させた溶液を30分かけて滴下した。次いでNa2CO3(14.3g)を水(54.9g)に溶解させた溶液を30分かけて滴下した。更に10%NaOH水溶液を滴下しpHを10.5に調整した。pHを10.5に保ちながら1時間熟成を行った。熟成終了後、反応物を吸引濾過した。沈澱を毎回450mlの水で3回洗った後、100℃にて乾燥した。乾燥終了物を軽く粉砕し750℃で1時間、空気中で焼成し、アルミナを担体とする銅−鉄−アルミニウム系触媒を得た。
Example 1
(Preparation of copper-iron-aluminum catalyst)
The following operation was performed to produce a copper-iron-aluminum catalyst having a copper / iron / aluminum atomic ratio of 1 / 0.8 / 1.8.
A reactor having a reflux condenser was charged with water (300 g), CuSO 4 .5H 2 O (48 g), FeSO 4 .7H 2 O (46.8 g) and aluminum hydroxide (12.8 g) while stirring. The temperature was raised to 96 ° C. The temperature was maintained at 95 ± 2 ° C. for 1 hour. Next, while maintaining this temperature, a solution of Na 2 CO 3 (44.8 g) dissolved in water (150 g) was added dropwise over about 80 minutes. A solution in which CuSO 4 .5H 2 O (4.8 g) and Al 2 (SO 4 ) 3 .16H 2 O (46.8 g) are dissolved in water (109.2 g) while maintaining the temperature at 95 ± 2 ° C. And a solution of Na 2 CO 3 (27.6 g) dissolved in water (98.2 g) were added dropwise at the same time. The aqueous solution of the metal salt was added dropwise over 60 minutes, and the aqueous solution of the alkaline substance was added dropwise over 30 minutes. A solution prepared by dissolving Al 2 (SO 4 ) 3 .16H 2 O (23.4 g) in water (53.5 g) was added dropwise thereto over 30 minutes. Then, a solution of Na 2 CO 3 (14.3 g) dissolved in water (54.9 g) was added dropwise over 30 minutes. Further, 10% NaOH aqueous solution was added dropwise to adjust the pH to 10.5. Aging was performed for 1 hour while maintaining the pH at 10.5. After completion of aging, the reaction product was filtered with suction. The precipitate was washed 3 times with 450 ml of water each time and then dried at 100 ° C. The dried product was lightly pulverized and calcined in the air at 750 ° C. for 1 hour to obtain a copper-iron-aluminum catalyst using alumina as a carrier.
(水素化分解)
攪拌機付きの500mLの鉄製オートクレーブに、上記の方法で得られた銅−鉄−アルミニウム系触媒10g、及びグリセリン200gを加え、水素置換した。その後、水素を液中に導入し、オートクレーブ内の圧力を2MPaに維持したまま、5L/min.(25℃、H2)で流通させつつ、加熱し、230℃にて反応させた。液相中の水分は、液中に導入される水素により、鉄製オートクレーブの上部に設けられた排出口から水蒸気として反応容器外に排出した。
反応経時サンプルおよび反応終了溶液は濾過後、カールフィッシャー分析により水分量を測定し、また下記条件のガスクロマトグラフィーにて分析し、生成物を定量し、これらの値から残存グリセリン(モル%)及び液相中のグリセリンから生じる全水分量を1としたときの水分の割合を求めた。また、経時的に測定した残存グリセリン量より一次反応速度定数kを算出し、これを反応速度の目安とした。これらの結果を表1に示す。
(Hydrocracking)
To a 500 mL iron autoclave with a stirrer, 10 g of the copper-iron-aluminum catalyst obtained by the above method and 200 g of glycerin were added, and hydrogen substitution was performed. Thereafter, hydrogen was introduced into the liquid, and the pressure in the autoclave was maintained at 2 MPa, and 5 L / min. The mixture was heated and allowed to react at 230 ° C. while flowing at 25 ° C. and H 2 . Moisture in the liquid phase was discharged out of the reaction vessel as water vapor from a discharge port provided at the top of the iron autoclave by hydrogen introduced into the liquid.
After the reaction time sample and the reaction end solution were filtered, the water content was measured by Karl Fischer analysis and analyzed by gas chromatography under the following conditions to quantify the product. From these values, residual glycerin (mol%) and The ratio of moisture when the total moisture generated from glycerin in the liquid phase was 1 was determined. Further, a first-order reaction rate constant k was calculated from the amount of residual glycerin measured over time, and this was used as a measure of the reaction rate. These results are shown in Table 1.
〔ガスクロマトグラフィー〕
カラム:Ultra-alloy キャピラリーカラム 15.0m×250μm×0.15μm(Frontier Laboratories 社製)、検出器:FID、インジェクション温度:300℃、ディテクター温度:350℃、He流量:4.6mL/min.
〔Gas chromatography〕
Column: Ultra-alloy capillary column 15.0 m × 250 μm × 0.15 μm (manufactured by Frontier Laboratories), detector: FID, injection temperature: 300 ° C., detector temperature: 350 ° C., He flow rate: 4.6 mL / min.
実施例2、3
実施例1で得られた触媒を用い、表1、表6に記載の条件にて水素化分解反応を実施した。すなわち、実施例2では水素流通条件の流量を実施例1における5L/min.から1L/min.に減じ、実施例3では、水素の流通方法を液中ではなく、反応溶液上部の気相部に導入し、気相中の水蒸気を反応容器外へ誘導することで、液相から水蒸気を気相へ供給させ、間接的に液相中の水分を除去した。結果を表1に示す。
Examples 2 and 3
Using the catalyst obtained in Example 1, hydrocracking reaction was carried out under the conditions described in Tables 1 and 6. That is, in Example 2, the flow rate under the hydrogen flow condition was 5 L / min. To 1 L / min. In Example 3, the hydrogen circulation method was introduced into the gas phase part above the reaction solution, not in the liquid, and the water vapor in the gas phase was guided out of the reaction vessel, so that the water vapor was removed from the liquid phase. It was made to supply to a phase and the water | moisture content in a liquid phase was removed indirectly. The results are shown in Table 1.
実施例4
(銅ラネー触媒)
日興リカ社製 銅ラネー触媒(品番RC-300)を用いた以外は、実施例1と同様に反応を実施した。
Example 4
(Copper Raney catalyst)
The reaction was carried out in the same manner as in Example 1 except that a copper Raney catalyst (product number RC-300) manufactured by Nikko Rica was used.
実施例5
(銅−亜鉛/酸化チタン触媒の調製)
反応器に硝酸銅(100g)と硝酸亜鉛(30g)を仕込み、水(2000g)に溶解した後、攪拌しながら昇温した。50℃で酸化チタン(33g)を仕込み、90℃で10質量%Na2CO3水溶液(546g)(金属塩と等モルのNa2CO3)を1時間で滴下し、1時間熟成した後、沈殿物を濾過・水洗し、110℃で10時間乾燥後、600℃で1時間焼成した。得られた金属酸化物は銅/亜鉛原子比が4/1で、担体としての酸化チタンに対する担持量が50質量%であった。この酸化チタン担持酸化銅−酸化亜鉛を触媒に用い、実施例1と同様に水素化分解反応を実施した。
実施例4及び実施例5の結果を表2に示す。
Example 5
(Preparation of copper-zinc / titanium oxide catalyst)
The reactor was charged with copper nitrate (100 g) and zinc nitrate (30 g), dissolved in water (2000 g), and then heated with stirring. Titanium oxide (33 g) was charged at 50 ° C., 10% by weight Na 2 CO 3 aqueous solution (546 g) (metal salt and equimolar Na 2 CO 3 ) was added dropwise at 90 ° C. over 1 hour, and after aging for 1 hour, The precipitate was filtered and washed with water, dried at 110 ° C. for 10 hours, and calcined at 600 ° C. for 1 hour. The obtained metal oxide had a copper / zinc atomic ratio of 4/1 and a supported amount with respect to titanium oxide as a support was 50% by mass. Using this titanium oxide-supported copper oxide-zinc oxide as a catalyst, a hydrogenolysis reaction was carried out in the same manner as in Example 1.
The results of Example 4 and Example 5 are shown in Table 2.
実施例6〜11
(銅/シリカ触媒)
触媒に、Cu/Siの原子比が1/0.55の日揮化学社製 銅/シリカ触媒(品番F01B)の粉砕品を用い、表3及び表4の条件にて水素化分解反応を実施した。実施例6〜9は、グリセリン100質量部に対して銅/シリカ触媒の使用量を5、2、1、0.5質量部と変化させ、実施例6、10、及び11は、反応温度を230、220、200℃と変化させて反応を実施し、それらの要因の影響を確認した。結果を表3及び表4に示す。
Examples 6-11
(Copper / Silica catalyst)
A hydrocracking reaction was carried out under the conditions shown in Tables 3 and 4 using a pulverized product of a copper / silica catalyst (product number F01B) manufactured by JGC Chemical Co., Ltd. having an atomic ratio of Cu / Si of 1 / 0.55. . Examples 6-9 change the usage-amount of a copper / silica catalyst with 5, 2, 1, 0.5 mass part with respect to 100 mass parts of glycerol, and Examples 6, 10, and 11 change reaction temperature. The reaction was carried out at 230, 220 and 200 ° C., and the influence of these factors was confirmed. The results are shown in Tables 3 and 4.
比較例1〜6
攪拌機付きの500mLの鉄製オートクレーブに、原料グリセリン200g、日揮化学社製 銅/シリカ触媒(品番F01B)の粉砕品をグリセリン100質量部に対して5質量部加え、水素置換した。表5及び表6に示すように、室温にて水素を1MPaまで導入し、表に記載の反応温度まで加熱したのち、水素圧を比較例1〜3においては6MPa、比較例4においては2MPa、比較例5及び6においては15MPaの圧力まで上げ、その後は水素を流通することなく密閉状態で、減少した圧力分は水素を補充することでその圧力を維持し、水素化分解反応を行った。なお、比較例2では原料のグリセリンに対する水分のモル比を1/1.3、比較例3及び6では100/20.5とした溶液を用いて反応を行った。
Comparative Examples 1-6
In a 500 mL iron autoclave with a stirrer, 200 g of raw material glycerin and a pulverized product of a copper / silica catalyst (product number F01B) manufactured by JGC Chemical Co., Ltd. were added in an amount of 5 parts by mass with respect to 100 parts by mass of glycerin, followed by hydrogen substitution. As shown in Table 5 and Table 6, after introducing hydrogen up to 1 MPa at room temperature and heating to the reaction temperature described in the table, the hydrogen pressure was 6 MPa in Comparative Examples 1-3, 2 MPa in Comparative Example 4, In Comparative Examples 5 and 6, the pressure was increased to 15 MPa, and after that, the hydrogen pressure was maintained in a sealed state without flowing hydrogen, and the reduced pressure was maintained by replenishing hydrogen to perform a hydrogenolysis reaction. In Comparative Example 2, the reaction was carried out using a solution in which the molar ratio of water to glycerol as a raw material was 1 / 1.3, and in Comparative Examples 3 and 6, 100 / 20.5.
同条件下にて使用した触媒の種類が異なる実施例1、4、5、6を比較してもっとも活性の高い銅/シリカ触媒を使用した実施例6を基準として、水素を流通させることなく反応液相中の水分を除去せずに反応させた比較例1に比べ、同様に反応温度230℃、触媒使用量がグリセリン100質量部に対して5質量部で、液相中の滞留水分を除去しながら反応させた実施例1〜6は、反応完結までに要した時間又は反応8時間目の残存グリセリン量から、グリセリンの反応性が向上しており、特に反応後期には、反応速度が向上する。加えて、実施例1〜6は1,2−PDの選択性も良好であった。また、実施例6と比較例1を比較すると、実施例6の方が選択性は向上している。表3、表4及び表5の結果より、銅/シリカ触媒の使用量が少ない実施例7〜8、反応温度の低い実施例10、11においても、比較例1に比べ、グリセリンの反応性が向上しており、特に反応後期は反応速度が速い。加えて、1,2−PDの選択性も良好であった。比較例1に比べて、触媒使用量が1/10である実施例9においては、反応後期は反応速度が速く、1,2−PDの選択性も良好であった。表3及び表5の結果より、反応温度、触媒使用量とも同じである実施例10と比較例4を比較すると、水分を除去した実施例10の方が反応完結までに要した時間は明らかに短く、かつ選択性は向上した。 Compared to Examples 1, 4, 5, and 6 in which the types of catalysts used under the same conditions were different, the reaction was carried out without passing hydrogen on the basis of Example 6 using the most active copper / silica catalyst. Compared to Comparative Example 1 in which the reaction was carried out without removing the water in the liquid phase, similarly, the reaction temperature was 230 ° C. and the amount of catalyst used was 5 parts by mass with respect to 100 parts by mass of glycerin. In Examples 1 to 6, the glycerin reactivity was improved from the time required until the completion of the reaction or the amount of residual glycerin at the 8th hour of the reaction, and the reaction rate was improved particularly in the later stage of the reaction. To do. In addition, Examples 1-6 also had good selectivity for 1,2-PD. Moreover, when Example 6 and Comparative Example 1 are compared, the selectivity of Example 6 is improved. From the results of Table 3, Table 4 and Table 5, in Examples 7 to 8 in which the amount of copper / silica catalyst used is small and in Examples 10 and 11 in which the reaction temperature is low, the reactivity of glycerin is higher than that in Comparative Example 1. In particular, the reaction rate is fast in the late reaction stage. In addition, the selectivity of 1,2-PD was also good. In Example 9, in which the amount of catalyst used was 1/10 compared to Comparative Example 1, the reaction rate was high in the late reaction period, and the selectivity for 1,2-PD was also good. From the results of Tables 3 and 5, comparing Example 10 and Comparative Example 4 in which the reaction temperature and the amount of catalyst used are the same, it is clear that the time required for Example 10 in which moisture was removed to complete the reaction was clear. Shorter and improved selectivity.
実施例12、13
実施例1と同じ、銅−鉄−アルミニウム系触媒を用い系内の水素圧力を15MPaとした実施例12、同様に水素圧を15MPaとし、日揮化学社製 銅/シリカ触媒(品番F01B)の粉砕品を用いた実施例13において、前記同様にグリセリンの水素化分解反応を行った。
表6に示すように、比較例5と比較して、反応液相中の滞留水分を除去しながら反応させた実施例12、13はグリセリンの反応性が向上しており、特に反応後期は反応速度が速い。加えて、実施例12、13は1,2−PDの選択性も良好であった。
Examples 12 and 13
Example 12 in which a copper-iron-aluminum-based catalyst was used and the hydrogen pressure in the system was 15 MPa, similarly, the hydrogen pressure was 15 MPa, and a copper / silica catalyst (product number F01B) manufactured by JGC Chemical Co., Ltd. was ground. In Example 13 using the product, the hydrogenolysis reaction of glycerin was performed in the same manner as described above.
As shown in Table 6, as compared with Comparative Example 5, Examples 12 and 13 reacted while removing the retained water in the reaction liquid phase had improved glycerin reactivity. The speed is fast. In addition, Examples 12 and 13 had good selectivity for 1,2-PD.
実施例14
攪拌機付きの500mLの鉄製オートクレーブに、日揮化学社製 銅/シリカ触媒(品番F01B)の粉砕品10g、及びグリセリン200gを加え、水素置換した。さらに室温にて水素を1MPaまで導入し、230℃まで加熱したのち、水素圧を15MPaの圧力まで上げ、密閉状態で、減少した圧力分は水素を補充することでその圧力を維持し、水素化分解反応を2時間行った。この時点では、加えたグリセリンの85.5モル%が反応し、反応液中の水分の割合は、グリセリンから生じる全水分量を1とするときの割合が0.93であった。
その後、鉄製オートクレーブを150℃まで冷却し、オートクレーブ内の圧力を1.5MPaに維持したまま、水素を液中に導入し、10L/min.(25℃、0.1MPa)で2時間流通させ、水分を除去した。その後、水素の流通を止め、230℃まで加熱し、水素圧を15MPaの圧力まで上げ、その後は水素を流通することなく密閉状態で、減少した圧力分は水素を補充することでその圧力を維持しつつ、再度水素化分解反応を行った。結果を表7に示す。
比較例5と比較して、反応途中で水分を除去した実施例14は水除去後にグリセリンの反応性が向上しており、1,2−PDの選択性も良好であった。
Example 14
To a 500 mL iron autoclave equipped with a stirrer, 10 g of a pulverized product of a copper / silica catalyst (product number F01B) manufactured by JGC Chemical Co., Ltd. and 200 g of glycerin were added and hydrogen-substituted. Furthermore, after introducing hydrogen up to 1 MPa at room temperature and heating to 230 ° C., the hydrogen pressure is increased to 15 MPa, and the reduced pressure is maintained by replenishing hydrogen in a sealed state. The decomposition reaction was carried out for 2 hours. At this time point, 85.5 mol% of the added glycerin reacted, and the ratio of water in the reaction solution was 0.93 when the total water content generated from glycerin was 1.
Thereafter, the iron autoclave was cooled to 150 ° C., and hydrogen was introduced into the liquid while maintaining the pressure in the autoclave at 1.5 MPa, and 10 L / min. (25 ° C., 0.1 MPa) was passed for 2 hours to remove moisture. Then stop the flow of hydrogen, heat up to 230 ° C, raise the hydrogen pressure to 15 MPa, and then keep the pressure in a sealed state without flowing hydrogen, replenishing the reduced pressure with hydrogen. However, the hydrocracking reaction was performed again. The results are shown in Table 7.
Compared with Comparative Example 5, in Example 14 in which water was removed during the reaction, the reactivity of glycerin was improved after water removal, and the selectivity of 1,2-PD was also good.
本発明によれば、水素化触媒の存在下に、多価アルコールと水素を接触させ、反応液相中の水を除去しながら行うことで、多価アルコールからのその水素化分解物、特にグリセリンからの1,2−PDの効率的な製造方法を提供することができる。特に本製造方法を用いることにより、工業的に実施が有利な低圧下で、グリセリンを効率的に転化させ、1,2−PDを選択性良く製造できる。 According to the present invention, the hydrogenolysis product from polyhydric alcohol, particularly glycerin, is obtained by contacting polyhydric alcohol with hydrogen in the presence of a hydrogenation catalyst and removing water in the reaction liquid phase. An efficient method for producing 1,2-PD from In particular, by using this production method, glycerin can be efficiently converted and 1,2-PD can be produced with good selectivity under a low pressure industrially advantageous.
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MYPI2010003406A MY182721A (en) | 2008-01-21 | 2009-01-08 | Method for producing hydrogenolysis product of polyhydric alcohol |
PCT/JP2009/050144 WO2009093486A1 (en) | 2008-01-21 | 2009-01-08 | Method for producing hydrogenolysis product of polyhydric alcohol |
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WO2009151021A1 (en) * | 2008-06-13 | 2009-12-17 | 三井化学株式会社 | Method for producing propylene glycol |
JP2013014577A (en) * | 2011-06-06 | 2013-01-24 | Daicel Corp | Method for producing hydrogenolysis product of erythritol |
US9447011B2 (en) | 2012-11-21 | 2016-09-20 | University Of Tennessee Research Foundation | Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol |
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